Molecular formation and electron correlation in HeH+

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Abstract
A one‐centre CI wave function for HeH+ reported by Stuart and Matsen for 0.1 ⩽ R ⩽ 5.0 has been analysed in detail from the viewpoint of molecular formation. Further, by means of a natural orbital analysis, it was possible to obtain some measure of the electron correlation contained within such wave functions for various R values. These effects were illustrated by means of a series of difference maps for the electron density. One‐ and two‐particle expectation values were obtained as a function of R. Thus, it was possible to study several aspects of the influence of the proton on the electron charge cloud as we pass from He through to the united atom Li+. The occupation numbers within the natural expansions were compared with those which arise from a similar analysis of a two‐centre wave function for HeH+. The “character” of such wave functions for HeH+, and also for He and Li+, were analysed and compared.